Bis-(2-azolyl) carbanilides



Patented Jan. 9, 1951 K I UNITED STATES PATENT OFFICE ms- (Z-AZOLYL)'CARBANILIDES Burt H. Carroll and Robert H. Sprague, Rochester, N. Y.,asslignors to Eastman Kodak Company, Rochester, N. Y., a corporation ofNew Jersey No Drawing. Application January 19, 1950,

, Serial No. 139,542

11 Claims. (01. 260-304) 1 2 This invention relates to new organiccommidity and substantially no absorption in the pounds useful asabsorbents of ultra-violet light Visible region of the spectrum. Theabsorbents and more particularly to bis-(Z-azolyDcarbaninaturally musthave solubility in Water or orlides and to a process for theirpreparation. ganic solvents used for incorporating them in the It isknown that color photographs on multi- 5 particular colloid layer. Oneof the commonest layer photographic material, particularly where defectsof compounds absorbing in the ultrathe dye images are formed insensitive emulsion violet region is that the compound is colored, layersby color development, are susceptible to usually yellow, or developssuch coloration upon fading and discoloration by the action ofultraexposure to ultra-violet light. Other compounds violet light towhich the photographs are subhave objectionable fluorescence underultrajected during viewing. It is also known that the violet light. Theresult is to alter the color of the residual couplers contained in theemulsion colored object seen through the overlying filter layers afterformation of the picture images in layer or packaging material. certainprocesses, are attacked by ultra-violet Various thiazoles,benzothiazoles and imidalight and form a stain which is undesirable inthe zoles are known which absorb in the ultra-violet finishedphotograph. The action of ultra-violet region, but previous to ourdiscovery none were light on finished color photographs is p'articuknownwhich possessed all of the desired proplarly noticeable in positiveprints on paper or erties set forth above. For example, 2-(p-aminootheropaque supports since this type of print phenyl)fi-methyl-benzothiazoleabsorbs in the deis frequently viewed in daylight Where there is a sir dre n o h p rum, and whil r a high content of ultra-violet radiation,colloid layers containing the compound are ini- It is also known thatcolor photographs, espetially; substantially colorless, exposure of thecially where the dye images are formed by color layers to ultra-violetlight cau e W g o development, can be protected from the fading thelayer. and discoloration caused by ultra-violet light by 5 We havediscovered a class of compounds havapplying to the finished colorphotograph a layer ing the desired properties of ultra-violet absorbofgelatin or other colloidal material having ents. The compounds are thebases or the quatherein an ultra-violet absorbing material. A ternizedsalts of bis-(2-azolyl)carbanilides repprocess of this type in whichaesculin, quinine, resented by the general formulas:

primuline, disalicylbenzidide, etc., are used as wherein Z representsthe non-metallic atoms necultra-violet absorbing materials in a gelatinover- 40 essary to complete a heterocyclic nucleus selected coatinglayer is described in British Patent from the group consisting of thebenzothiazol, 565,929. Salminen et al., U. S. application Serial thiazoland imidazol series, D represents the non- No. 91,422, filed May 4,1949, discloses another metallic atoms necessary to complete amonoprocess for applying ultra-violet absorbents to nuclear arylradical, n represents a positive inphotographic prints. teger of from 1to 10, and n represents a positive It is also known to incorporateultra-violet abinteger of from 1 to 2, R represents an alkyl sorbents insheeting such as thin films of gelagroup and X represents an acidradical. tin, cellulose esters, resins, etc., in order to pro-Accordingly, it is one of the objects of our invide photographicfilters, or transparent wrapvention to provide a new class of compoundsand ping materials for the protection of foodstuffs a process forpreparing them. Another object is dyed textile and similar materialsfrom theefto provide colloid layers containin the comfects ofultra-violet light. pounds suitable for use for filtering out ultra- Inthe mentioned and other uses the ultraviolet radiations. A furtherobject is to provide violet absorbents must possess, among otherele'mentsprotected against ultra-violet light by properties, goodstability to light, heat and humeans of colloid lay r n ai ing theabsorb- 3 ents. Other objects will become apparent from considerationsof the following description of our invention.

According to the process of preparing our compounds we react a di-acidchloride, e. g., phosgene, oXalyl, malonyl, succinyl, glutaryl or adipylchlorides, etc. with a Z-(p-aminophenyDazole such as aZ-(p-aminophenyl)-benzothiazole, -thiazole or -imidazole etc., to formthe corresponding bis-compound of formula above. Suitable azoles are:

Benzothz'azoles The benzothiazoles can have other substituents on thenuclei in addition to or'in place of those indicated such as halogen,ethyl, propyl, etc.

Thiazoles 2- minophenylthiazole 2- minophenyll-phenylthiazoleZ-p-aminophenyl-4-sulfophenylthiazole Z-p-amino-rn-sulfophenylthiazole2-p-aminophenyl-4-methylthiazole I midazoles 2-p-aminophenylimidazole 2-p-aminophenyl-4-phenylimidazole 2 -p-aminophenyl-4-methylimidazole 2-p-amino-m-sulfoph enylimidazole 2-p-aminophenyl-5-methylimidazole SOaNa be reacted directly by heating with our new bases to give usefulquaternary salts include dimethylsulfate, diethylsulfate, methylbenzenesulfonate, ethyl benzenesulfonate, n-propyl benezenesulfonate,methyl p-toluenesulfonate, ethyl p-toluenesulfonate, n-propylp-toluenesulfonate, n-butyl p-toluenesulfonate, isobutylp-toluenesulfonate, sec-n-butyl p-toluenesulfonate, n-amylp-toluenesulfonate, etc. Compounds wherein X in the above formularepresents a bromide ion or an iodide ion can conveniently be preparedby interacting a quaternary salt of our bis-compounds,

such as the dimetho-p-toluenesulfonate, with a solution of potassiumbromide and potassium iodide, respectively. Compounds where X representsa perchlorate (010-4) ion can advantageously be prepared by interactinga quaternary salt of our bis-compounds, such as thedimetho-p-toluenesulfonate, with a solution of sodium perchlorate.Compounds where X represents a chloride ion can conveniently be obtainedby interacting a quaternary salt where X represents an iodide ion with amethanol suspension of silver chloride. Other methods of preparing ournew quaternary ammonium compounds can be used, if desired. Such methodsare commonly employed and are Well known to those skilled in the art.For example, compounds where X represents a halide ion can be preparedby heating our new free bases with the appropriate alkyl halide in asealed tube.

The following examples will serve to further illustrate the manner inwhich we practice our invention.

Example I.-4,4' bis (6 methyl 7 sulfa-2- benzothiazolyl) carbamlidedisodium salt SOsNa s s l on ONH 0/ om The thiazoles and imidazoles mayhave other substituents in addition to or in place of those indicated,e. g., halogen, in the 4 and 5 positions and the oand m-positions of thephenyl group.

The quaternary ammonium salts of our invention are obtained by treatmentof the benzothiazole, thiazole and imidazol free bases of thebiscompounds, for example, with an alkyl ester of p-toluenesulionicacid. A method for preparing quaternary ammonium compounds of our newbases comprises treating one of the alkyl sulfuric or sulfonic acidester addition salts of our new bases with an inorganic salt in asolvent (water or alcohol) (i. e., by double decomposition). Thequaternary addition compounds made from the bis-azole bases have thestructure wherein R is an alkyl group such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, secn-b utyl, amyl, etc., and X is an anion(or acid radical), such as halide (e. g., 01*, Br, I), perchlorate(0104), thiocyano (SCN-), alkylsulfate (e. g., CH3SO-4),benzenesulfonate (CSH5SOZOT), p-toluenesulfonate (-p- CH3C6H4SO20 etc.Typical esters which can One hundred grams of 2-p-aminophenyl-6-methyl-7sulfobenzothiazole sodium salt are dissolved in 4 liters of hotwater, 50 grams of sodium carbonate monohydrate are added and a currentof phosgene gas is passed into the solution with -stirring and heatingon the steam bath. Durover calcium chloride. The yield of nearlycolorless material is 95 g., 9 The product is purified byrecrystallization from methyl alcohol cc. per gram). The yield ofpurified material is 71.6 g., 69%. A solution of one part in 150,000 inwater in a 1 cm. layer gives a maximum density of .74 at 347 m The freeacid form is obtained by neutralizing with mineral acid.

neutralizing with mineral acid.

thiazolyl) adipanilidedisodium salt benzothiazo-lyD-carbanilide, 7.6 g.(2 .mols. plus some SONa s i 1 I to i s onoONn-w-oHi-oHr-(mr-cHr-co-Nn-Oo A. mixture of 17 .5 g. of2-aminophenyl-6- excess) of methyl p-toluene-sulionate and 50methyl-7-sulfobenzothiazo1esodium salt and -300 10 cc. of nitrobenzenewere refluxed together for cc. of chlorobenzene is heated to the boilingpoint 310 mlinutes, cooled, and thieoclea iI solumition poured and 10cc. of triethylamine are added. An ex- 8 wy n o 500 cc. of ace he. he 'xure was cess (8 g.) of adipylchloride is added in small a w d t rys allz v rn ht a d th p odportions with stirring. A vigorous reaction takeuct collected on a filter, washed on the filter with place and stickyorangesolid separates out of the acetone F recrystalllzed from 1500 8-mixture at once. The mixture is boiled and ethyl alcohol The yield of Py fl' Crystals stirred for one hour, chilled and the solvent dewascanted. The residue is stirred with two 50 cc. The gsfi d1eth'ethy15u1fate was portions of acetone and finally dissolved in 400 Preparedslmllally glsmg of methyl sulfate cc. of. warmwater and filtered. Theproduct is 3 22 g i 23;? ;f$f g: ig g g fgggg g 2 25.- f ggmfgggg gggggstirred with several 200-cc. portions of ether until talline andfiltered off. After recrystalliza- The yield of yellow crystals is 9.0g. The product is purified by solution in water and salting out 25 :3 gg g f the meld of yellow with sodium chloride. The yield of purified mapr terial is 2.8 g. A solution of one part 'in 50,000 in ExampleV.4,4-bis-(G-methyZ-Z-benaothiazolwater in a 1 cm. layer gives a maximumdensity ill) -carbamluie CH U NHCONH 0 CH O, O Q) of 1.27 at 324 ma. Thefree acid is obtained by A mixtu eo .0 mo of -D-a no--o-dichloroberizehe was stirred and heated on the ExampleIII.'4,4'-bis-(6-methyl-7-suljo-2-bensteam bath until solution wascomplete. Phoszothz'azolyl) -2, Zf0carbmtilide te tm 80-- gene gas wasthen passed'into the solution with dium salt i i 40 stirring and'heatingfor one hour until a sample some some s i /s t 0H.- 0H. OQ-NHC o-NH o\N/ OsNa OIN8 g N A mixture of 44.4 g. (2mols) of 2-(p-amino-m gave anegative diazo test. The solution wassulfophenyl)-6-methyl-7-sulfobenzothia2tole dichilled to 25, the solidproduct collected on a sodium salt (prepared by the method disclosed insuction filter, washed on the filter with cc. of FIAT Report 1016, p.17), 25 g. of sodium bicar- 50 o-dichlorobenz'ene, and dried. The yieldof yelbonate and 9 l. of water was heated on the steam low crystals was26.5 g. Soluble impurities were bath with stirring. A current ofphosgenegas removed by extraction with 300 cc. of hot pyrwas passed into the hotsolution with stirringior idine. The yield of colorless purifiedmaterial 8 hours, additional 25-g. quantities of sodium biwas 19.0 g.carbonate being added at 2-hour intervals. The Other bis-compounds ofour invention can be next day phosgene was againpassed in for, 8"Obtained in the manner of the above examples hours and 250 g. of sodiumbicarbonate added in by treatment of the selected pam n0ph ny fiveportions. After standing at room temperaazole with one of the mentioneddiacid chlorides.

phenyl-G-mthyl benzothiazole and 400 cc. of

ture overnight the mixture was filtered with suc- AS pr y mentioned,theflompolmds o the.

tion and the damp filter cake was dissolved in 4 1; inv nti n ar u fu icolloid filter ay s f all of hot water. The solution was stirred andheated k h u for Protecting photographic on the steam bath with 15 g. ofNorite decolorl r prin it s preferred to t at he prints izing carbon,filtered and the product salted out the m n cri in the Salminen etal.inwith 250 g. of sodium chloride. The product was with ue solutions f onof the absorbers n recrystallized from 3500 cc. of methyl alcohol.Vention- Alternately, the 1 p t n be The yield of colorless crystals was12.4 g. coated with a colloid layer n ng the absorber, e. g., adispersion of the, sodium salt of Example IV.--4,4'-bis-(3,6-dimethyl-2-benzothi the absorber, or a quaternized derivative, inaqueazolz'um) -carbam'lide di-p-toluenesulfonate ous'gelatin solutio canbe coated onto the print.

0113- CHI O NH CO..NH C

cm sor-o-oimcih 3 ci soio-caiiom A 7 We also include as a part of ourinvention incorporating the novel absorbers into a lpre-sensitizedcolor-film or paper. In this case the absorber is preferably applied asa separate colloid layer to the .emulsion coated product and thoseabsorbers, e. e. that of Example V, which arerelatively insoluble inprocessing solutions are preferred for this purpose. The quaternaryammo- 8 "the non-metallic atoms necessary 'to complete a mononucleararyl radical, n represents a positive integer of from 1 to 10 and nrepresents a positive integer from 1 to 2, R represents an alkyl groupand X represents anacid radical.

2. A compound selected from those represented by the general formulas:

wherein X represents the non-metallic atoms nium derivatives areespecially useful in those necessary to complete a heterocyclic nucleussecases where organic solvents especially alcohols, acetone, etc., areused for applying a colloid layer (e. g. cellulose ester) containing theabsorber to the object to be protected from ultraviolet lected from thegroup consisting of the benzothiazol, .thiazol and imidazol series, Drepresents the non-.metallic atoms necessary to complete a mononucleararyl radical, R represents an alkyl light. Similarly, the quaternizedcompounds are 25 group and X represents an acid radical.

preferred for use in making transparent sheeting such as celluloseacetate, since it is most 3. A compound selected from those representedby the general formulas wherein Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus selected from the groupconsisting of the benzothiazol, thiazol and imidazol series, Drepresents the nonmetallic atoms necessary to complete a mononucleararyl radical, n represents a positive integer from 1 to 10, R representsan alkyl group, and X represents an acid radical.

4. A compound selected from those represented by thegeneral formulas:

1. A compound selected from those represented by the general formulas:

wherein X represents the non-metallic atoms necessary to complete aheterocyclic nucleus of wherein Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus selected from the groupconsisting of the benzothiazol, thiazol and imidazol series, Brepresents I,

the benzothiazol series, D represents the nonmetallic atoms necessary tocomplete an aryl group of the benzene series, B represents an alkylgroup and X represents an. acid radical.

2,587,877 9 l0 5. A compound selected from those represented 7. Thecompound: 4,4-bis-(6-znethy1-7-su1foby the general formulas:z-benzothiazolyl) carbanilide disodium salt.

wherein Z represents the non-metallic atoms 8. The compound:4,4'-bis-(6-methyl-7-su1fonecessary to complete a heterocyclic nucleusof 2-benzothiazoly1)-2,2-disu1fo carbanilide tetra the thiazol series, Drepresents the non-metallic sodium salt.

atoms necessary to complete an aryl group of 9. The compound:4,4'-bis-(G-methyl-I-sulfothe benzene series, R represents an alkylgroup 2-benzothiazoly1) adipanilide disodium salt.

and X represents an acid radical. 10. The compound:4,4'-bis-(3,6-dimethy1-2- 6. A compound selected from those representedbenzothiazolium) -carbani1ide di-p-toluenesulfowherein Z represents thenon-metallic atoms nec- 11. The compound: 4,4'-bis-(G-methyl-Z-benessaryto complete a heterocyclic nucleus of the zothiazolyl) -carbanilide.

imidazol series, D represents the non-metallic BURT H. CARROLL. atomsnecessary to complete an aryl group of the ROBERT H. SPRAG-UE. benzeneseries, B represents an alkyl group and 35 X represents an acid radical.No references mted Certificate of Correction Patent No. 2,537,877January 9,1951 BURT H. CARROLL ET AL. It is hereby certified that errorappears in the printed specification of the above numbered patentrequiring correction as follows:

Column 5, line 9, for Qaminophenyl read Q-p-amz'nopkenyl; column 6, line63, strike out the Words with aqueous solutions of one of the absorbersin and insert the same before the manner in line 62, same column;columns 7 and 8, claim 1, for that portion of the first formula readingand that the said Letters Patent should be read as corrected above, sothat the same may conform to the record of the case in the PatentOffice.

Signed and sealed this 27th day of March, A. D. 1951.

[SEAL] THOMAS F. MURPHY,

Assistant Gammz'ssz'oner of P :ants.

1. A COMPOUND SELECTED FROM THOSE REPRESENTED BY THE GENERAL FORMULAS: